We examine some of the structural aspects that influence the mesomorphic behavior of liquid-crystalline dimeric epoxy resins with imine groups in the mesogens. We synthesized two new series of monomers and compared them with previously synthesized monomers. Compared with previously studied series, the imine group in the new monomers is oriented differently with respect to the ether and ester groups linked to the end of the mesogenic unit. Our results confirmed the importance of polarization of the mesogenic groups and the presence of an ester group in the inner position in the formation of smectic mesophases. By curing with primary and tertiary amines, we demonstrate that these two requirements are necessary if liquid-crystalline thermosets are to be obtained with different degrees of order. These studies were carried out with differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction. (C) 2003 Wiley Periodicals.